United States Patent [191 [11] Patent Number: 4,863,636 Chang et 21. [45] Date of Patent: Sep. 5, 1989

[54] SUBSTITUTED [56] References Cited N-HYDROXYPHTHALIMIDES AND THEIR U.S. PATENT DOCUMENTS USE AS DETERGENT ADDITIVES 3,767,671 10/1973 Klebe et a1...... 548/473 [75] Inventors: Laurence W. Chang, Orange, Conn.; 3,915,879 10/1975 Barnett et al...... 560/37 Robert G. Fischer, Stevensville, Primary Examiner-Paul Lieberman Canada Assistant Examiner-Christine A. Skane [73] Assignee: American Cyanamid Company, Attorney, Agent, or Firm-Steven H. Flynn Stamford, Conn. [51] ABSTRACT [21] Appl. No.: 156,131 N-hydroxyimide compounds derived from substituted phthalic anhydride are provided which exhibit strong [22] Filed: Feb. 12, 1988 metal ion chelating ability, making them useful as deter [51] Int. Cl.4 ...... C11D 3/28; C07D 209/48 gent additives, in boiler water systems, as reaction inter [52] US. Cl...... 252/542; 252/544; mediates, etc. A detergent composition containing N 252/ 545; 252/546; 548/473; 548/475; 560/37; hydroxyimide and/or carboxy hydroxamic acid deter 562/450; 562/430 gent additives is also disclosed. [58] Field of Search ...... 548/473, 475; 560/ 37; 562/450, 430; 252/542, 544, 545', 546 9 Claims, No Drawings 4,863,636 1 2 These and other objects are achieved, according to SUBSTITUTED N-HYDROXYPHTHALHVIIDES the present invention, by compounds having the for AND THEIR USE AS DETERGENT ADDITIVES mula

The present invention relates to chelating agents (I) which are useful as adjuvants for detergents and to detergent compositions, particularly fabric-washing detergent compositions. In particular it relates to novel N-hydroxyimide compounds having good transition metal ion chelating properties and to detergent compo sitions comprising at least one detersive surfactant and an effective amount of an N-hydroxyimide detergent additive. wherein R is carboxy, sulfo, or caroxyalkyl or sulfonal kyl having 1-12 carbon atoms, or alkali metal salts BACKGROUND OF THE INVENTION thereof; and X is hydroxy or ——O"M+, where M+ is an Detergent compositions have long employed materi alkali metal cation (i.e., Li+, Na+, K+, etc.). als, known as “builders”, to improve the detergency of Also contemplated are ring-opened derivatives of the soaps and synthetic detergents by actively chelating the Formula I compounds, which have the formula alkali metal cations which are normal components of “hard” tap water. Such builders have been found to (II) affect, for instance, soil suspension, emulsi?cation of II soil particles, solubilization of water-insolubles, and inactivation of various mineral constitutents present in a detergent system. Many materials useful as builders have been proposed, and their effects are known. See, ll e.g., US. Pat. Nos. 3,852,213, 3,950,260, 4,182,718, and OH 4,440,646 (all incorporated herein by reference). Recently, however, the attention of detergent manu wherein X and R are as de?ned above. facturers and researchers has turned.to the role of Also contemplated herein are detergent compositions heavier metal cations, i.e., transition metal cations, in comprising one or more detersive surfactants and one the formation of stain complexes on fabrics and other or more detergent additives consisting essentially of surfaces. It has been observed that these multivaleut N-hydroxyphthalimide compounds having the formula transition metal cations, particularly iron (Fe+++, en hance the binding of the components of many stains to 0 0 substrates, and breaking up the cation-enhanced bonds II II is an effective approach to stain removal. Therefore, X there is a strong need for the discovery of new materials R N-X or R that are effective as chelating agents for transition metal III-X cations, are easy to prepare, and can be added to deter as 1'. H gent compositions in economical amounts to boost stain-removing power. It has now been discovered that certain cyclic N where X and R are as defined above. hydroxyimide compounds derived from substituted DETAILED DESCRIPTION OF THE phthalic anhydride are active metal ion chelants and are 45 INVENTION useful as detergent additives. The N-hydroxyphthali mides of the present invention are water-soluble and The N-hydroxyimide detergent additives of the pres form soluble chelates with transition metal ions which ent invention are advantageously prepared by reacting a hinder detergent action and form stain complexes on substituted phthalic anhydride with hydroxylamine or a fabrics and other substrates. In basic solutions, e.g., 5 O salt thereof to obtain the N-hydroxyimides of the pres above about pH 9, ring-opened derivatives of the N ent invention. The substituted N-hydroxyimide com hydroxyphthalirnides are believed to be produced, pounds may be further reacted in the presence of base to yielding carboxy hydroxamic acid-functional deriva obtain ring-opened substituted mono-hydroxamated tives which are active metal ion chelants as well. phthalic acid. Thus, a typical reaction scheme for the 55 preparation of detergent additives according to the SUMMARY OF THE INVENTION present invention is as follows: It is therefore an object of the present invention to provide a new class of metal ion chelating agents. 0 It is a further object of the present invention to pro II vide new detergent additives which are active in stain 60 removal. ' R O substituted phthalic It is a further object of the present invention to pro anhydride vide a detergent additive free of phosphorus. It is a further object of the present invention to pro vide a novel detergent composition. 65 It is a further object of the present invention to pro H2NOH hydroxylamine vide a fabric-washing detergent composition that is effective in stain removal. 4,863,636 4 -continued compounds, and the variety of spacings possible (from 0 molecule to molecule) between the functional groups, II may enhance the metal chelating effectiveness of the compounds by allowing them to sequester a wider vari R N-OH substituted N-hydroxy ety of cations. phthalimide The N-hydroxyimide compounds and derivatives are active stain removers and are advantageously included in a detergent composition, in accordance with the present invention. A detergent composition of this in OH“ vention will contain at least one detersive surfactant. Such surfactants will be present in amounts usually encountered in detergent compositions, e. g., from about 0 ll 1 to about 50% by weight, preferably about 5 to about 25% by weight for fabric-washing detergents, and most OH 15 R substituted mono preferably from about 10 to about 20% by weight based N-OH hydroxamated phthalic on the total weight of the detergent composition. The H acid surfactants may be anionic, nonionic, cationic or am 0 H photeric, and mixtures of different detersive surfactants may be used. Non-limiting examples of suitable deter Phthalic anhydride is a well-known intermediate in sive surfactants include: the manufacture of, e. g., inks and synthetic resins. Many (a) Anionic surfactants: soaps, i.e., alkali metal (pref substituted phthalic anhydrides suitable for use in the erably sodium or potassium) salts of long-chain fatty present invention are also known. Carboxy-substituted acids containing from 8 to 20 carbon atoms, such as phthalic anhydride, e.g., 1,3-dioxo-5-phthalancarboxy lauric, myristic, oleic, palmitic, capric, caprylic, and lic acid (“trimellitic anhydride”), is a well-known inter stearic acids, used singly or in mixtures of differing mediate in the preparation of resins, adhesives, poly chain lengths; alkali metal salts of organic sulfuric reac mers, dyes and printing inks. The substituted phthalic tion products having long hydrocarbon chains of about anhydride compounds suitable for use in preparing the 8 to about 20 carbon atoms and a radical selected from N-hydroxyphthalimide compounds of the present in the group consisting of sulphonic acid and sulfuric acid vention will have terminal carboxylic acid or sulfonic ester radicals, such as sodium or potassium alkyl sul acid groups bonded directly or by a C1-C1; alkylene phates, preferably those obtained by sulphating higher bridging group to the benzene ring of the phthalic anhy dride moiety. Carboxy-substituted phthalic anhydride (C3-C3) alcohols; sodium or potassium alkyl benzene and sulfo-substituted phthalic anhydride are preferred. sulphonates in which the alkyl group contains from Reaction of the substituted phthalic anhydride to 35 about 9 to about 20 carbon atoms, such as sodium linear obtain N-hydroxyimide products may be accomplished alkyl (Clo-C15) secondary benzenesulphonate, 2-phe by contacting the substituted phthalic anhydride with at nyl-dodecanesulphonate, 2-phenyl-octadecanesulphon least an equimolar quantity of hydroxylamine or a salt ate and 3-phenyl-dodecanesulphonate; alkali metal thereof, preferably hydroxylamine hydrochloride. The (preferably sodium) ole?n sulphonates, i.e., the mixture reaction will normally be carried out in the presence of 40 of detersive surfactants obtained from sulphonation of about 2-5 moles per mole of hydroxylamine of a basic Cg-Cgz olefins, preferably straight-chain alpha-ole?ns; agent, preferably an organic base such as sodium meth sodium alkyl glyceryl ether sulphonates, including oxide, sodium ethoxide, sodium acetate, pyridine, trieth ethers of higher alcohols derived from tallow coconut ylamine, or quinoline. Most preferably, the reaction will oil and synthetic alcohols derived from petroleum; so be carried out in an alcoholic solvent, such as methanol 45 dium coconut oil fatty acid monoglyceride sulphates or ethanol. and sulphonates; sodium or potassium salts of sulfur The product may be isolated in any one of a number acid esters of the reaction between higher fatty alcohols of known ways. For example, the product can be iso (e.g., tallow or coconut oil alcohols) and ethylene ox lated by precipitation from a non-solvent, such as hex ide; the esteri?cation products of fatty acids with isethi ane, and the precipitate ?ltered, washed and dried onic acid, neutralized with sodium hydroxide; and so under vacuum to give the N-hydroxyimide product. dium or potassium salts of fatty acid amides of methyl Alternatively, ?ash or spray drying may be used. The taurine. drying step removes substantially all of the organic (b) Nonionic synthetic detersive surfactants: com base, and washing with alcoholic hydrogen chloride pounds formed by condensing ethylene oxide with a effectively scavenges residual amounts, in cases where 55 hydrophobic base formed by the condensation of prop complete removal of the basic agent is required. ylene oxide with propylene glycol; the polyethylene In basic solution, as discussed previously, it is be oxide condensates of alkyl-phenols, e.g., the condensa lieved that the N-hydroxyphthalimides of the present tion products of alkyl-phenols, having an alkyl group invention undergo a ring-opening reaction to at least containing from about 6 to 12 carbon atoms in either a some degree. Therefore, detergent additives according 60 straight or branched chain, with ethylene oxide, said to this invention may comprise substituted N-hydrox-= ethylene oxide being present in amounts equal to 5 to 25 yphthalimides (unopened form) and substituted mono= moles of ethylene oxide per mole of alkyl-phenols (the hydroxamated phthalic acid moieties (opened form), as alkyl substituent in such compounds may be derived seen in Formulas I and II, supra. Alkali metal salts, from polymerised propylene, diisobutylenc, octene do especially sodium salts, of the substituted N-hydroxyph 65 decene, or nonene, for example); compounds derived thalimides and their carboxy hydroxamic acid deriva from the condensation of ethylene oxide with the prod tives are also contemplated. The multiple functionality uct resulting from the reaction of propylene oxide and of the N-hydroxyimide and carboxy hydroxamic acid ethylenediamine, such as compounds containing from 4,863,636 5 6 about 40% to about 80% polyoxyethylene by weight group, such as 3-(N,N-dimethyl-N-hexadecylamrnoni and having a molecular weight of from about 5,000 to o)propane-l-sulphonate, 3-(N,N-dimethyl-N-hex about 11,000 resulting from the reaction of ethylene adecylammonio)-2-hydroxypropane-l-sulphonate, 3 oxide groups with a hydrophobic base constituted of (dodecylmethylsulphonium) propane sulphonate, and the reaction product of ethylenediamine and excess 3-(cetylmethylphosphonium) ethane sulphonate. propylene oxide, said hydrophobic base having a mo The detergent compositions of the present invention lecular weight of the order of 2,500 to 3,000; the con will contain, besides one or more detersive surfactants, densation product of aliphatic alcohols having from 8 to about 3% to about 12% by weight of the composition, 18 carbon atoms, in either straight chain or branched preferably about 6% by weight, of the N-hydroxyimide chain con?guration, with ethylene oxide, e.g., a coco and/or the carboxy hydroxamic acid detergent addi‘ nut alcohol-ethylene oxide condensate having from 6 to tives described above. 30 moles of ethylene oxide per mole of coconut alcohol, In addition to the surfactants and the N-hydroxyi the coconut alcohol fraction having from 10 to 14 car mide and/or carboxy hydroxamic acid compounds, the bon atoms; long chain tertiary amine oxides correspond detergent composition according to the invention may ing to the following general formula, wherein also contain conventional detergent builders such as R1R2R3N:O, wherein R1 is an alkyl radical of from condensed phosphates, trisodium nitrilotriacetate about 8 to 18 carbon atoms and R2 and R3 are each (NT A), sodium carbonate, zeolites, sodium silicates, methyl, ethyl or hydroxyethyl radicals, such as dime etc., and organic polymers such as polyacrylates, poly thyldodecylamine oxide, dimethyloctylamine oxide, methacrylates, and polymaleates. See, e.g., US. Pat. dimethyldecylamine oxide, diethyltetradecylamine 20 Nos. 3,392,150, 3,666,664, 3,707,502, 3,839,215 and U.S. oxide and dimethylhexadecylamine oxide, N-bis (hy Pat. No. 4,067,816, all of which are incorporated herein droxyethyl)dodecylamine oxide; long chain tertiary by reference. -The combined detergent builders will phosphine oxides corresponding to the following for make up from about 10% to about 50% by weight of the mula R4R5R6P:O, wherein R4 is an alkyl, alkenyl, or detergent composition, preferably about 20% to 40% monohydroxyalkyl radical of 10 to 18 carbon atoms and 25 by weight. R5and R6 are each alkyl or monohydroxyalkyl groups In addition to the essential detersive surfactants and containing from 1 to 3 carbon atoms, such as dimethyl detergent additives, a detergent composition of the dodecylphosphine oxide, dimethyltetradecylphosphine invention may comprise such conventional ingredients oxide, ethylmethyltetradecylphosphine oxide, cetyl as lather boosters ,(e.g., alkanolamides), ?llers, an dimethylphosphine oxide, dimethylstearylphosphine tiredeposition agents, ?uorescers, pigments, germicides, oxide, cetylethylpropylphosphine oxide, diethyl scents, and enzymes. dodecylphosphine‘ oxide, diethyltetradecylphosphine A detergent composition according to the invention oxide, bis(hydroxymethyl)dodecylphosphine oxide, can be prepared by any conventional manufacturing bis(2-hydroxyethyl)dodecylphosphine oxide, 2-hydrox technique used for preparing detergent compositions, ypropylmethyltetradecylphosphine oxide, dime such as slurry making and spray-drying, and the deter thyloleylphosphine oxide, and dimethyl-Z-hydrox gent can take anyone of the common physical forms ydodecylphosphine oxide; and dialkyl sulphoxides cor associated ‘with detergents, such as powders, ?akes, responding to the following formula, R7R8S=0, granules, noodles, cakes, bars and liquids. wherein R7 is an alkyl, alkenyl, beta- or gamma Liquid detergent compositions according to the in monohydroxyalkyl radical or an alkyl or beta- or gam 40 vention will most preferably be concentrated aqueous ma-monohydroxyoxyalkyl radical containing one or solutions having a basic pH, at least about pH 9, com two other oxygen atoms in the chain, the R7 groups prising one or more of the detersive surfactants de ranging from 10 to 18 carbon atoms in chain length, and scribed above and one or more of the N-hydroxyimide wherein R8 is methyl, ethyl or alkylol, such as dodecyl or carboxy hydroxamic acid detergent additives of this methyl sulphoxide, tetradecyl methyl sulphoxide, 3 45 invention. hydroxytridecyl methyl sulphoxide, 2-hydroxydodecyl The invention is further illustrated by the following methyl sulphoxide, 3-hydroxy-4-decyloxybutyl methyl examples, which should not be construed as limiting the sulphoxide, 3-hydroxy-4-dodecyloxybutyl methyl scope of the invention. sulphoxide, 2-hydroxy-3-decyloxypropyl methyl sulph oxide, 2-hydroxy-3-dodecyloxypropyl methyl sulphox EXAMPLE 1 ide, dodecyl ethyl sulphoxide, 2-hydroxydodecyl ethyl A mixture of 10.78 g of hydroxylamine hydrochlo sulphoxide, dodecyl-2-hydroxy ethyl sulphoxide. ride and 40 ml of methanol was heated in a 55° C. oil (c) Ampholytic synthetic surfactants: derivatives of bath until a clear solution was obtained. The oil bath aliphatic secondary and tertiary amines, in which the was removed and 35 ml of sodium methoxide solution aliphatic radical may be straight chain or branched (8.68 g sodium methoxide in 30 ml of methanol) was chain and wherein one of the aliphatic substituents con added to the solution. The mixture was stirred at room tains from about 8 to 18 carbon atoms and one contains temperature for 30 minutes with occasional cooling in a an anionic water solubilizing group, such as sodium-3 water bath to maintain the temperature of the mixture dodecylaminopropionate, sodium3-dodecylaminopro below 35° C. panesulphonate and sodium N-2-hydroxydodecy-N 60 The mixture was then ?ltered, and to the ?ltrate methyl-taurate. cooled in an ice-salt bath was added 19.74 g of trimel (d) Zwitterionic synthetic surfactants: litic anhydride. The mixture was stirred in the ice-salt derivatives of aliphatic quaternary ammonium com bath for a fgw minutes, then warmed slowly to room pounds, sulphonium compounds and phosphonium temperature. compounds in which the aliphatic radical may be 65 The anhydride was not soluble in the reaction mix straight or branched chain and wherein one of the ali ture; however as the reaction proceeded, the reaction phatic substituents contains from about 8 to 18 carbon mixture turned to a clear solution. After stirring over atoms and one contains an anionic water solubilizing night a yellow.- wet cake was obtained. 4,863,636 7 8 Infrared (IR) spectroscopic analysis of the reaction A sample of the compound of Example 1 was tested mixture indicated that reaction with the hydroxylamine and showed very good tea stain removal capability had taken place. High pressure liquid chromatography when compared with a control detergent solution in (HPLC) indicated that most of the product was cyclic N-hydroxyimide. which no detergent additive was used. The reaction mixture containing the product was It will be understood that the foregoing description of ?ltered. The solid collected was washed with methanol the invention is susceptible to modi?cations, changes and vacuum dried; 12.5 g of dried solid was obtained. and adaptations, all of which are intended to be compre hended within the meaning and range of equivalents of EXAMPLE 2 10 the appended claims. For instance, though the forego To 300 ml of a 50% aqueous 4-sulfophthalic anhy ing description is directed to the use of the N-hydroxyi dride solution was added 24.43 g of NaOH. The mixture mides in detergent systems, they will also ?nd applica turned to a dark red solution after a few minutes. The tion in boiler water systems and other scale prevention solution was then stripped of water in a rotary evapora uses, polymerization intermediates, and other embodi tor, and 200.2 g of a light pink solid residue were ob ments where strong metal ion chelation is required. tained after vacuum drying at 60° C. The light pink solid product was then heated in a We claim: vacuum oven at 150° C. for 7 hours. IR analysis indi 1. A detergent composition comprising an effective cated that the solid had been converted to 4-sulfoph amount of one or more detersive surfactants and an thalic anhydride. A mixture of 280 ml of methanol and 20 effective amount of one or more chelating agents con 41.8 g of hydroxylamine hydrochloride was heated in a sisting essentially of substituted N-hydroxyimide com 60“ C. oil bath until the hydroxylamine salt was dis pounds having the formula solved. The oil bath was removed and 153 ml of a meth anol solution (containing 33.5 g sodium methoxide) were added. The mixture was stirred at room tempera 25 ture for 15 minutes, then stirred in an ice water bath for X 15 minutes, and then ?ltered. N-X or R The ?ltrate was cooled in an ice water bath and 100 g of the synthesized 4-sulfophthalic anhydride was III-X ll H added. The reaction mixture was stirred overnight, and 30 0 the ice water bath was allowed to warm to room tem perature. wherein R is carboxy, sulfo, C1-C1; carboxyalkyl or A dark orange solution containing some solid was sulfoalkyl, or alkali metal salts of any of the foregoing, obtained. The mixture was ?ltered, and about 10 g of and X is —OH or —O-M+, where M+ is an alkali white solid were collected. 35 metal cation. The ?ltrate was then concentrated to about 350 ml 2. A detergent composition according to claim 1 and an equal amount of anhydrous diethyl ether was added. A large amount of precipitate appeared. The wherein said substituted N-hyroxyimide compound is precipitate was collected by ?ltration and then vacuum selected from the group consisting of N-hydroxy-S-car dried at 80° C. About 55 g of N-hydroxyimide (most of 40 boxy-phthalimide, N-hydroxy-S-sulfo-phthalimide, 1,4 it in the unopened form) was obtained. dicarboxy-2-hydroxamobenzene, l-hydroxamo-2, 4 carboxy-benzene, 1-carboxy-2-hydroxamo-4-sulfo-ben~ EXAMPLE 3 zene, l-hydroxarno-2-carboxy-4-sulfobenzene, alkali The performance of the N-hydroxyimide compound metal salts thereof, and mixtures thereof. of Example 1 as a fabric-washing detergent additive was 45 3. A detergent composition according to claim 1, examined in a tea stain removal test: wherein said detersive surfactant is an anionic surfac Swatches of white cotton cloth were boiled in very tant, a non-ionic synthetic surfactant, or a combination strong tea (1O tea bags/1 liter dionized water, brewed 10 of anionic and non-ionic surfactants. min.) for 15 minutes. The tea solution and swatches were removed from the heat and cooled to 115° F. with 4. A detergent composition according to claim 1, stirring. The swatches were thereafter wrung and air wherein the detersive surfactant is a soap or mixture of dried between paper towels. soaps. Dionized water was heated to 40° C. and 0.1 g of 5. A detergent composition according to claim 1, CaClz were added per each liter of water, followed by wherein the detersive surfactant is a non-ionic synthetic 1.5 g per liter of water of a commercial fabric-washing surfactant, or a combination of non-ionic synthetic sur detergent (Tide ®; Procter & Gamble). factants. To l-liter aliquots of this detergent solution were 6. A detergent composition according to claim 1 in added 100 mg of the detergent additives to be tested, the form of a concentrated aqueous solution having a which were stirred until dissolved. The wash solutions pH of at least 9. were maintained at about 35° C. and a stirring speed of 7. A detergent composition according to claim 1, 100 rpm. The pH was adjusted to 10 if necessary with sulfuric acid or sodium hydroxide. Tea stained swatches which-further includes lather boosters, ?llers, an of cloth were added to each test solution and stirred tiredeposition agents, ?uorescers, pigments, germicides, rapidly for 10 minutes, after which the solution was scents, enzymes, or conventional detergent builders. poured off and the swatches squeezed out and rinsed for 8. A detergent composition comprising one or more 2 minutes in dionized water containing the same propor detersive surfactants comprising about 1% to 50% by tion of CaCg. The swatches were then air dried over weight of the total composition and one or more substi night and compared against a control solution. tuted N-hydroxyimide compounds having the formula 4,863,636 9 10 and X is —~OH or —O"M+, where M+ is an alkali O metal cation, said substituted N-hydroxyimide com 1 n pounds comprising about 3% to 12% by weight of the X R N-X or R total composition. N-X 9. A detergent composition according to claim 7, n u k‘; wherein the combined detergent builders comprise from about 10% to 50% by weight of the total deter wherein R is carboxy, sulfo, C1-C1; carboxyalkyl or gent composition. sulfoalkyl, or alkali metal salts of any of the foregoing, * it It * *

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